1. Iron Coordination Properties of Gramibactin as Model for the New Class of Diazeniumdiolate Based Siderophores
- Author
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Silvio Sammartano, Sofia Gama, Demetrio Milea, Ron Hermenau, Winfried Plass, Christian Hertweck, and Mariachiara Frontauria
- Subjects
Siderophore ,Full Paper ,010405 organic chemistry ,Chemistry ,Chemical speciation ,Real systems ,siderophores ,Organic Chemistry ,Inorganic chemistry ,diazeniumdiolate ,iron(III) coordination ,General Chemistry ,Rhizosphere bacterium ,Full Papers ,chemical speciation ,sequestering ability ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Paraburkholderia graminis - Abstract
Gramibactin (GBT) is an archetype for the new class of diazeniumdiolate siderophores, produced by Paraburkholderia graminis, a cereal‐associated rhizosphere bacterium, for which a detailed solution thermodynamic study exploring the iron coordination properties is reported. The acid‐base behavior of gramibactin as well as its complexing ability toward Fe3+ was studied over a wide range of pH values (2≤pH≤11). For the latter the ligand‐competition method employing EDTA was used. Only two species are formed: [Fe(GBT)]− (pH 2 to 9) and [Fe(GBT)(OH)2]3− (pH≥9). The formation of [Fe(GBT)]− and its occurrence in real systems was confirmed by LC‐HRESIMS analysis of the bacteria culture broth extract. The sequestering ability of gramibactin was also evaluated in terms of the parameters pFe and pL0.5. Gramibactin exhibits a higher sequestering ability toward Fe3+ than EDTA and of the same order of magnitude as hydroxamate‐type microbial siderophores, but smaller than most of the catecholate‐type siderophores and much higher than the most known phytosiderophores., The sequestration properties of gramibactin as a prototype for the new class of diazeniumdiolate siderophores is presented and compared with siderophores derived from catecholates and hydroxamates. According to pFe and pL0.5 values, gramibactin is a considerably more potent sequestering agent than the known class of phytosiderophores and approximately reaches the ability of typical hydroxamates like desferrioxamines.
- Published
- 2021
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